O-(1-substituted-3-methyl-4-chloropyrazolo)-thionophosphoric(phosphonic)acid esters

ABSTRACT

O-(1 - SUBSTITUTED - 3 - METHYL - 4 - CHLORO-PYRAZOLO)THIONOPHOSPHORIC (PHOSPHONIC) ACID ESTERS OF THE FORMULA   1-R&#34;,3-(H3C-),4-CL,5-(R&#39;&#39;O-P(=S)(-R)-O-)-PYRAZOLE   IN WHICH R IS AN ALKYL OR ALKOXY RADICAL OF 1 TO 6 CARBON ATOMS, R&#39;&#39; IS ALKYL OF 1 TO 6 CARBON ATOMS, AND R&#34; IS ALKYL OR CYANOALKYL WHEREIN THE ALKYL RADICAL HAS 1 TO 6 CARBON ATOMS, OR PHENYL, WHICH POSSESS INSECTICIDAL AND ACARICIDAL PROPERTIES.

United States Patent US. Cl. 260310 R 7 Claims ABSTRACT OF THEDISCLOSURE O-(l substituted 3 methyl 4 chloro-pyrazolo)-thionophosphoric (phosphonic) acid esters of the formula in which R isan alkyl or alkoxy radical of 1 to 6 carbon atoms,

R is alkyl of l to 6 carbon atoms, and

R" is alkyl or cyanoalkyl wherein the alkyl radical has 1 to 6 carbonatoms, or phenyl,

which possess insecticidal and acaricidal properties.

The present invention relates to and has for its objects the provisionof particular new O-(1-substituted-3-methyl-4-chloropyrazolo)-thionophosphoric (phosphonic) acid esters, i.e.0,0-dialkyl-O-(1-alkyl-, cyanoalkylor phenyl- 3-methyl 4 chloropyrazolo)-thiono phosphoric acid esters and their alkanephosphonic acidester analogues, which possess insecticidal and acaricidal properties,active compositions in the form of mixtures of such compounds with solidand liquid dispersible carrier vehicles, and methods for producing suchcompounds and for using such compounds in a new way especially forcombating pests, e.g. insects and acarids, with other and furtherobjects becoming apparent from a study of the within specification andaccompanying examples.

It is known from U.S. Patent Specification 2,754,244 that0,0-dia1kyl-O-pyrazolo-(thiono)phosphoric, for example 0,0-dimethyl-(Compound A) or 0,0-diethyl-O- [3-methyl-pyrazol-5-yl]thionophosphoricacid ester (Compound B), possess insecticidal properties.

The present invention provides, as new compounds, theO-pyrazolothionophosphoric(phosphonic) acid esters of the formula R S Umll RO NN it" 1) in which R is an alkyl or alkoxy radical of 1 to 6carbon atoms,

R is alkyl of 1 to 6 carbon atoms, and

R is alkyl or cyanoalkyl wherein the alkyl radical has 1 to 6 carbonatoms, or phenyl.

In the formulatl), R is preferably a straight-chain or branched loweralkyl or alkoxy radical of 1 to 4 carbon atoms, R is preferablystraight-chain or branched lower alkyl of 1 to 4 carbon atoms, and R" ispreferably cyanoethyl, methyl, ethyl or phenyl.

Surprisingly, the O pyrazolothionophosphoric (phosphonic) acid estersaccording to the invention display a Patented July 23, I 1 974 higherinsecticidal and acaricidal action than compounds of the prior art. Thenew compounds have proved particularly valuable in combating pestsharmful to health and pests of stored products. Furthermore, some of thecompounds display a surprisingly low toxicity towards warmbloodedanimals. They thus represent a genuine enrichment of the art.

The present invention also provides a process for the preparation of an'O pyrazolo-thionophosphoric (phosphonic) acid ester of the formula (I)in which a pyrazole derivative of the formula no NN in which R" has theabove-mentioned meaning,

Cl CH3 acid- S I binding ll agent (CzH50)2P-Cl H0 -EJI (Ha) I (IIIa) S('11 CH:

ll (CzH50)gP-O- The pyrazole derivatives of the formula (II), which arerequired as starting materials, have hitherto not been described in theliterature, but can be prepared as follows:

Starting from ethyl acetoacetate and substituted hydrazines, thecorresponding pyrazolones are obtained, which are converted by means ofsulfonylchloride into the chlorinated compounds, which then react withtrialkylphosphites to give the hydroxypyrazole derivatives of theformula (II) (Va) (VI) NN (VII) l S02 C1 Cl CH3 Cl Cl CH3 (VIII)Examples of the pyrazole derivatives (11) are 1-methyl-, l-ethyland1-cyanoethyl-3-methyl-4-chl0ro-S-hydroxypyrazoles.

As examples of thionophosphoric (phosphonic) acid ester halides (III),there may be mentioned: 0,0-dimethyl-, 0,0-diethyl-, 0,0-di-n-propyl,0,0-di-isopropyl, 0,0-di-n-butyl, 0,0-di-isobutyl,;0,0-di-sec.-butyl0,0-ditert.-butyl, O-methyl-O-ethyl andO-ethyl-O-isobutylthiono-phosphoric acid ester halides, and alsoO-methyl-, O-ethyl-, O-n-propyl-, O-isopropyl-, O-n-butyl-, O-isobutyl-O-tert.-butyl and O-sec.-butylmethane-, -ethane-, -propaneand-butanethionophosphonic acid ester halides.

The preparative process is preferably carried out with the use of asuitable solvent or diluent. Practically any inert organic solvent canbe used for this purpose, especially an aliphatic or aromatic optionallychlorinated hydrocarbon, such as benzene, toluene, xylene, benzine,methylene chloride, chloroform, carbon tetrachloride or chlorobenzene,an ether, such as diethyl ether, dibutyl ether or dioxane, a ketone, forexample acetone, methyl ethyl ketone, methyl isopropyl ketone ormethylisobutyl ketone, or a nitrile, such as acetonitrile orpropionitrile.

Any customary acid acceptor can be used as the acid binding agent.Alkali metal carbonates and alcoholates, such as sodium and potassiumcarbonate, methylate and ethylate, and also aliphatic, aromatic andheterocyclic amines, for example triethylamine, dimethylamine, dimethylaniline, dimethylbenzylamine and pyridine, have proved particularlysuitable.

The reaction temperatures can be varied over a substantial range. Ingeneral, the reaction is carried out at about to 100 C., preferablyabout 20 to 70 C.

The reaction is generally carried out at normal pressure.

To carry out the process, the starting substances are in most casesemployed in equimolar ratios. An excess of one or other reactant doesnot produce any significant advantages. The reaction is preferablycarried out in the presence of one of the above-mentioned solvents andin the presence of an acid acceptor, at the indicated temperatures, andafter stirring for several hours the reaction mixture is worked-up inthe usual mannerwith warming if appropriate.

The substances according to the invention are mostly obtained in theform of colorless to slightly colored oils which cannot be distilledwithout decomposition but can be freed of the last volatileconstituents, and thus purified, by so-called slight distillation, thatis to say prolonged heating under reduced pressure to moderatelyelevated temperatures. The substances are generally characterized by therefractive index; however, some of the products are obtained ascrystalline compounds having a sharp melting point.

As has already been mentioned, the new O-pyrazolothionophosphoric(phosphonic) acid esters are distinguished by an excellent insecticidaland acaricidal activity against plant pests, pests harmful to health andpests of stored products. They possess a good action both againstsucking and against biting insects and mites (Acarina). At the same timethey show a low phytotoxicity and some of the compounds show anextremelylow toxicity towards warm-blooded animals. The LD on oral administrationto rats is between 500 and 1,000 mg./ kg. for some of the compoundsaccording to the invention.

For these reasons, the compounds according to the invention may besuccessfully employed as pesticides in plant protection and protectionof stored products, and also in the hygiene field.

To the sucking insects contemplated herein there belong, in the main,aphids (Aphidae) such as the green peach aphid (Myzus persicae), thebean aphid (Doralis fabae), the bird cherry aphid (Rhopalosiphum padi),the pea aphid (Macrosiphum pisi) and the potato aphid (Macrosiphumsolanifolii), the currant gall aphid (Cryptomyzus korschelti), the rosyapple aphid (Sappaphis malt), the mealy plum aphid (Hyalopterusarundinis) and the cherry black-fly (Myzus cerasi); in addition, scalesand mealybugs (Coccina), for example the oleander scale (Aspidiotushederae) and the soft scale (Lecanium hesperidum) as well as the grapemealybug (Pseudococcus maritimus); thrips (T hysanoptera), such as Hercinothrips femoralis, and bugs, for example the beet bug (Piesmaquadrata), the red cotton bug (Dysdercus intermedius), the bed bug(Cimex lectularius), the assassin bug (Rhodnius prolixus) and Chagas bugT riatoma infestans) and, further, cicadas, such as Euscelis bilobatusand Nephotettix bipunctatus; and the like.

In the case of the biting insects contemplated herein, above all thereshould be mentioned butterfly caterpillars (Lepidoptera) such as thediamond-back moth (Plutella maculipennis), the gypsy moth (Lymantriadispar), the brown-tail moth (Euproctis chrysorrhoea) and tentcaterpillar (Malacosoma neustria); further, the cabbage moth (Mamestrabrassicae) and the cutworm (Agrotis segetum), the large white butterfly(Pieris brassicae), the small winter moth (Cheimatobiw brumata), thegreen oak tortrix moth (Tortrix viridana), the fall armyworm (Laphygmafrugiperda) and cotton worm (Prodenia litura), the ermine moth(Hyponomeuta padella), the Mediterranean flour moth (Ephestiakiihniella) and greater wax moth (Galleria mellonella); and the like.

Also to be classed with the biting insects contemplated herein arebeetles (Coleoptera), for example the granary Weevil (Sitophilusgranarius=Calandra granaria), the Colorado beetle (Leptinotarsadecemlineata), the dock beetle (Gastrophysa viridula), the mustardbeetle (Phaedon cochleariae), the blossom beetle (Meligethes aeneus),the raspberry beetle (Byturus tomentosus), the bean weevil (BruchidiusAcanthoscelides obtectus), the leather beetle (Dermestes frischi), thekhapra beetle (Trogoderma granarium), the flour beetle (Triboliumcasraneum), the northern corn billbug (Calandra or Sitophilus zeamais),the drugstore beetle (Stegobium paniceum), the yellow mealworm (Tenebriomolitor) and the saw-toothed grain beetle (Oryzaephilus surinamensis),and also species living in the soil, for example wireworms (Agriotesspec.) and larvae of the cockchafer (Melolontha melolontha);cockroaches, such as the German cockroach (Blattella germanica),American cockroach (Periplanem amerz'cana), Madeira cockroach(Leucophaea or Rhyparobia maderae), oriental cockroach (Blattaorientalis), the giant cockroach (Blaberus giganteus) and the blackgiant cockroach (Blaberus fuscus) as well as Henschoutedenia flexivitta;further, Orthoptera, for example the house cricket (Acheta domesticus);termites such as the eastern subterranean termite (Reticulitermesflavipes) and Hymenoptera such as ants, for eX- ample the garden ant(Lasius niger); and the like.

The Diptera contemplated herein comprise essentially the flies, such asthe vinegar fly (Drosophila melanogaster), the Mediterranean fruit fly(Ceratitis capitata), the house fly (Musca domestica), the little housefly (Farmia canicularis), the black blow fly (Phormia regina) andbluebottle fly (Calliphora erythrocephala) as well as the stable fly(Stomoxys calcitrans); further, gnats, for example mosquitoes such asthe yellow fever mosquito (Aedes aegypti), the northern house mosquito(Culex pipz'ens) and the malaria mosquito (Anopheles stephensi); and thelike.

With the mites (Acari) contemplated herein there are classed, inparticular, the spider mites (Tetranychidae) such as the two-spottedspider mite (T etranychus telarius=Tetmnychus althaeae or T etranychusurticae) and the European red mite (Paratetranychu pil0sus=Panonychusulmi), gall mites, for example the black currant gall mite (Eriophyesribis) and tarsonemids, for example the broad mite (Hemitarsonemuslatus) and the cyclamen lapsing fever tick (Ornithodorus mowbata); andthe like.

When applied against hygiene pests and pests of stored products,particularly flies and mosquitoes, the compounds of the invention arealso distinguished by an outstanding residual activity on wood and clay,as well as a good stability to alkali on limed substrates.

The active compounds according to the instant invention can be utilized,if desired, in the form of the usual formulations or compositions withconventional inert (i.e. plant compatible or herbicidally inert)pesticide diluents or extenders, i.e. diluents, carriers or extenders ofthe type usable in conventional pesticide formulations or compositions,e.g. conventional pesticide dispersible carrier vehicles such as gases,solutions, emulsions, suspenions, emulsifiable concentrates, spraypowders, pastes, soluble powders, dusting agents, granules, etc. Theseare prepared in known manner, for instance by extending the activecompounds with conventional pesticide dispersible liquid diluentcarriers and/ or dispersible solid carriers optionally with the use ofcarrier vehicle assistants, e.g. conventional pesticide surface-activeagents, including emulsifying agents and/or dispersing agents, whereby,for example, in the case where water is used as diluent, organicsolvents may be added as auxiliary solvents. The following may bechiefly considered for use as conventional carrier vehicles for thispurpose: aerosol propellants which are gaseous at normal temperaturesand pressures, such as freon; inert dispersible liquid diluent carriers,including inert organic solvents, such as aromatic hydrocarbons (e.g.benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated,especially chlorinated, aromatic hydrocarbons (e.g. chlorobenzenes,etc.), cycloalkanes (e.g. cyclohexane, etc.), paraflins (e.g. petroleumor mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g.methylene chloride, chloroethylenes, etc.), alcohols (e.g. methanol,ethanol, propanol, butanol, glycol, etc.) as well as ethers and estersthereof (e.g. glycol rnonomethyl ether, etc.), amines (e.g.ethanolamine, etc.), amides (e.g. dimethyl formamide, etc.), sulfoxides(e.g. dimethyl sulfoxide, etc.), acetonitrile, ketones (e.g. acetone,methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.),and/or Water; as well as inert dispersible finely divided solidcarriers, such as ground natural minerals (e.g. kaolins, clays, alumina,silica, chalk, i.e. calcium carbonate, talc, attapulgite,montmorillonite, kieselguhr, etc.) and ground synthetic minerals (e.g.highly dispersed silicic acid, silicates, e.g. alkali silicates, etc.);whereas the following may be chiefly considered for use as conventionalcarrier vehicle assistants, e.g. surface-active agents, for thispurpose: emulsifying agents, such as non-ionic and/or anionicemulsifying agents (e.g. polyethylene oxide esters of fatty acids,polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkylsulfonates, aryl sulfontaes, etc., and especially alkyl arylpolyglycolethers, magnesium stearate, sodium oleate, etc.); and/or dispersingagents, such as lignin, sulfite waste liquors, methyl cellulose, etc.

Such active compounds may be employed alone or in the form of mixtureswith one another and/or with such solid and/or liquid dispersiblecarrier vehicles and/or with other known compatible active agents,especially plant protection agents, such as other insecticides andacaricides, or rodenticides, fungicides, bactericides, nematocides,herbicides fertilizers, growth regulating agents, etc., if desired, orin the form of particular dosage preparations for specific applicationmade therefrom, such as solutions, emulsions, suspensions, powders,pastes, and granules which are thus ready for use.

As concerns commercially marketed preparations, these generallycontemplate carrier composition mixtures in which the active compound ispresent in an amount substantially between about (11-95% by weight, andpreferably 05-90% by weight, of the mixture, whereas carrier compositionmixtures suitable for direct application or field application generallycontemplate those in which the active compound is present in an amountsubstantially between about 0.0001-10%, preferably 0.11%, by weight ofthe mixture. Thus, the present invention contemplates over-allcompositions which comprises mixtures of a conventional dispersiblecarrier vehicle such as (1) a dispersible inert finely divided carriersolid, and/or (2) a dispersible carrier liquid such as an inert organicsolvent and/or water preferably including a surface-active effeclowingexamples:

tive amount of a carrier vehicle assistant, eg a surfaceactive agent,such as an emulsifying agent and/or a dispersing agent, and an amount ofthe active compound which is effective for the purpose in question andwhich is generally between about 0.0001%, and preferably 01-95%, byweight of the mixture.

The active compounds can also be used in accordance with the well knownultra-low-volume process with good success, i.e. by applying suchcompound if normally a liquid, or by applying a liquid compositioncontaining the same, via very effective atomizing equipment, in finelydivided form, e.g. average particle diameter of from 50- microns, oreven less, i.e. mist form, for example by airplane crop sprayingtechniques. Only up to at most about a few liters/hectare are needed,and often amounts only up to about 15 to 1000 g./hectare, preferably 40to 600 g./hectare, are suflicient. In this process it is possible to usehighly concentrated liquid compositions with said liquid carriervehicles containing from about 20 to about 95% by weight of the activecompound or even the 100% active substance alone, eg about 20100% byweight of the active compound.

Furthermore, the present invention contemplates methods of selectivelykilling, combating or controlling pests, e.g. insects and acarids, whichcomprises applying to at least one of correspondingly (a) such insects,(b) such acarids, and (c) the corresponding habitat thereof, i.e. thelocus to be protected, a correspondingly combative or toxic amount, i.e.an insecticidally or acaricidally effective amount, of the particularactive compound of the invention alone or together with a carriervehicle as noted above. The instant formulations or compositions areapplied in the usual manner, for instance by spraying, atomizing,vaporizing, scattering, dusting, watering, squirting, sprinkling,pouring, fumigating, andthe like.

It will be realized, of course, that the concentration of the particularactive compound utilized in admixture with the carrier vehicle willdepend upon the intended application. Therefore, in special cases it ispossible to go above or below the aforementioned concentration ranges.

The synthesis, unexpected superiority and outstanding activity of theparticular new compounds of the present invention are illustrated,without limitation, by the fol- EXAMPLE 1 LT test for Diptera Testinsects: Musca domestica Solvent: acetone 2 parts by weight of activecompound are dissolved in 1000 parts by volume of solvent. The solutionso ob tained is diluted with further solvent to the desired lowerconcentrations.

2.5 ml. of the solution of active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test insects are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test insects is periodically observed. The timewhich is necessary for a 100% destruction is determined.

The test insects the active compounds, the concentra tions of the activecompounds and the periods of time at which there is a 100% destructioncan be seen from the following Table 1:

TABLE 1 wu test for Diptcra) Active compound concentration of thesolution Active compounds in percent LTiou (A) CH 0.2 8 70% ll(CII30)2PO NN H (known) (B) C H3 0. 2 105 i 0.02 6 75 2, (C H O) P-O NNH (known) 11 01 on; 0.2 30' l I 0. 02 75 0.002 81128071; ((1 H O )2P-OIII-N CH3 (5) Cl C 11 0. 2 60 i-CaII: O\fi I D. 02 85 P o I CH3 III-N(6) o1 CH3 0. 2 30 C2H5 S l 0. 02 110' [I 0.002 9 .30%

(3 11 0 IIIN EXAMPLE 2 LT test for Diptera Test animals: Aedes aegyptiSolvent: acetone 2 parts by weight of the active compound are dissolvedin 1000 parts by volume of the solvent. The solution so obtained isdiluted with further solvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test insects are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test insects is continuously observed. The timewhich is necessary for a 100% destruction is determined.

The active compounds, the concentrations of the active compounds, thetest insects and the periods of time at which there is a destruction canbe seen from the following Table 2:

TABLE 2 ioo test for Diptem) Active compound concentrations of the solu-Active compounds tionin percent LT m A). CH 0.2 3 2309 i I (CI'I30)2PO HI |IN H (known) (13)..." 9H: 0.2 180 ll (C H50)2P-O IIIN II (known) (11)C1 CH3 0.2 60 0. 02 60 H 0.002 305007 (CH30)zPO (1) C1 CH3 0. 2 (30 S II 0. 02 (30 I 0.002 180 (CQILSO)? 1 O ITTN CH3 (6) 01 CH: 0.2 60 C2115 II 0. 02 60' 0. 002 180 0.0002 3 -=0o% CzHaO IIIN (4)... Cl CH3 0.2 69 Sl 0. 02 H 0. 002 (0111 0) PO l CHz-CIIz-CN EXAMPLE 3 LDm test Testinsects: Sitophilus granarius Solvent: acetone 2 parts by weight ofactive compound are dissolved in 1000 parts by volume of solvent. Thesolution so obtained is diluted with further solvent to the desiredlower concentrations.

2.5 ml. of the solution of active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test insects are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after thecommencement of the experiments. The destruction is determined as apercentage.

The test insects, the active compounds, the concentrations of the activecompounds and the results can be seen from the following Table 3:

TABLE 3 (LDioo test) Active compound concentrations of Destructhesolution tion in Active compounds in percent percent 10 (A) CH; 0.2 o

i a0)2P-O N N H (known) (B) 0H. 0.2 100 u 0. 02 0 (CIH50)2P O NN H(known) 11 Cl (H 0. 2 100 S s 0. 02 100 II 5 0. 002 0 3O) 2 --0- I-|I IH C a (l) 01 ("Hg 0. 2 100 S 0. 02 90 H 0.002 (CzH5O)zP-O If- I (5) ClCH: 0. 2 100 aH10\fi 006?); 10g

/P0 0H, III- v 40 (6).---- 01 CH: 0.2 100 CzHs S 0. 02 100 ll 0. 002 0/PO CzH5O I}!- I (4) Cl CH: 0.2 100 0. 02 100 ll 0. 002 0 (CH30)2POCHz-C Hz-C N Cl (H 0. 2 100 i 0.02 100 [I 0.002 0 2HsO)2 CHr-CHz-C N(10)---. Cl (Hz 0.2 100 CzHz S 0. 02 100 0. 002 95 P-O- 05 CHz-CHz-CN CCH 0. 2 100 l i 0. 02 100 II 0. 002 0 50) 2 0- 10 EXAMPLE 4 L'Dmo testTest insects: Blatta orientalis Solvent: acetone 2 parts by weight ofactive compound are dissolved in 1000 parts by volume of solvent. Thesolution so obtained is diluted with further solvent to the desiredconcentrations.

2.5 ml. of the solution of active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test insects are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after thecommencement of the experiments. The destruction is determined as apercentage.

The active compounds, the concentrations of the active compounds, thetest insects and the results can be seen from the following Table 4:

TABLE 4 (LDioo test) Active compound concentrations of Destructhesolution ticn in Active compounds in percent percent (A) C Ha 0. 2 0

i l (CHaO)nPO-( H NN H (known) (B) CH; 0. 2 H O. 02 0 (C3H50)7P0 NN H(known) (11) 01 CH; 0. 2 100 S I l 0. 02 100 ll 0.002 60 (0 H30) zP'-Oll I-N CH3 (1) Cl CH: 0. 2 100 S I l 0. 02 100 H 0.002 0 (C1H50)2P-O' I|I-N C 2 (5) 01 CH: 0. 2 100 i-C H O S l 0. 02 100 ll 0. 002 100 P-O- 0.0002 60 CH; NN

(6) Cl CH 0. 2 100 C2H5 S l 0. ()2 100 0.002 30 C H O IIIN EXAMPLE 5LDmo test Test insects: Ornithodorus moubata (Nymphs) Solvent: acetone 2parts by weight of the active compound are dissolved in 1000 parts byvolume of the solvent. The solution so obtained is diluted with furthersolvent to the desired concentrations.

2.5 ml. of the solution of the active compound are pipetted into a Petridish. On the bottom of the Petri dish there is a filter paper with adiameter of about 9.5 cm. The Petri dish remains uncovered until thesolvent has completely evaporated. The amount of active compound persquare meter of filter paper varies with the concentration of thesolution of active compound used. About 25 test insects are then placedin the Petri dish and it is covered with a glass lid.

The condition of the test insects is observed 3 days after thecommencement of the experiments. The destruction is determined as apercentage.

The active compounds, the concentrations of the active compounds, thetest insects and the results can be seen from the following Table 5:

TABLE 5 (LDmo test) Active compound concentrations Destrucof thesolution tion in Active compounds in percent percent (A). CH; 0.2 40

i I (CHaO)2PO-- (known) (1) C1 CE. 0.2 100 s o. 04 100 ll 0. 008 100(CzH50)2P-O 0. 0016 60 1]IN CH5 (5) Cl CH 0. 2 100 l-CzHyO S I i 0. 04100 ll 0.00s 02 C Ha Il1-N (6) CaHa Cl (H5 0. 2 100 S 0. 04 100 II 0. s0 /PO C2H5O I|T-- N (His (4)....... 01 CH: 0.2 100 |SI 0.04 0 (C H302P--O- 111* J CHz-C H -GN (2) 01 CH; 0.2 100 S I l 0. 04 100 H 0. 00s 20(O1H 0)1P-O 1TI-N CHg-CHg-ON (7).-. Cl CH3 0.2 100 i-C H7O\fi I 0. 04 20P--O CH: IITN CHg-CHg-CN (10)-.-. Cl CH: 0.2 100 0211K? I 0. 04 8O 0 110 III-N CH;C Hr-CN TABLE 5Continued Active compound concentrationsDestrucot the solution tion in Active compounds in percent percent(3)--. Cl CH3 0.2 i, l 0. 04 60 (01130) P-O- (12)..... C1 CH: 0. 2 100 Sl 0. 04 100 II 0. 008 so (CgH50) P-O- (8) Cl CH: 0.2 100 i-C aH10\ i3 0.04 60 r -o- C E; III J (9)......: Cl CH: 0. 2 100 Cal-15 S 0. 04 20EXAMPLE 6 Mosquito larvae test Test insects: Aedes aegypti Solvent: 99parts by weight acetone Emulsifier: 1 part by weightbenzylhydroxydiphenyl polyglycol ether To produce a suitable preparationof active compound, 2 parts by Weight of the active compound aredissolved in 1000 parts by volume of the solvent containing the amountof emulsifier stated above. The solution thus obtained is diluted withwater to the desired lower concentrations.

The aqueous preparations of the active compounds are placed in glassvessels and about 25 mosquito larvae are then placed in each glassvessel.

After 24 hours, the degree of destruction is determined as a percentage.100% means that all the larvae are killed. 0% means that no larvae atall are killed.

13 The active compounds, the concentrations of the active compounds, thetest insects and the results can be seen from Table 6:

TABLE 6 (Mosquito larvae test) Active com- Degree pound conofdecentrationsot struction the solution in 3 Active compounds in ppm.percent .04-.- on, 10

(CHa)2PO-- I NN H (known) (11).-.- 01 CH; 10 100 S l l 1 100 0.1 0(CHa0)aPO- III-L (1) Cl CH: 10 100 i 1 70 (C2Hs0)a I 1 M CHa l-CaH1O\S o1 100 1 0 P o J CH3 N- (6)..--. Cl CH: 10 100 /P-0 C2 5O IIII\ (4) 01(Hz 10 100 1 100 II 0.1 0

' I (CHaO)zP-O CH2CHz-CN '2 c1 om 10 100 i 1 90 (C2 s )2 I II CHz-CHz-CN(7)- 01 CH: 10 100 l-O;H O\fi 1 0 4. /P o I OH: ITI N CHz-CHr-CN(10)..-. 01 CH; 10 100 7 02B; i I 1 4o otmo f" CHr-CHz-CN (3)-.-.. 01CH; 10 100 S 1 100 II 0.1 30 (CH30)2P-O EXAMPLE 7 Phaedon larvae testSolvent: 3 parts by weight acetone Emulsifier: 1 part by weightalkylaryl polyglycol ether To produce a suitable preparation of activecompound, 1 part by weight of the active compound is mixed with thestated amount of solvent containing the stated amount of emulsifier, andthe concentrate is diluted with water to the desired concentration.

Cabbage leaves (Brassica oleracea) are sprayed with the preparation ofthe active compound until dripping wet and then infested with mustardbeetle larvae (Phaedon cochleariae) 1 After the specified periods oftime, the degree of destruction is determined as a percentage: meansthat all the beetle larvae are killed. 0% means that none of the beetlelarvae are killed.

The active compounds, the concentration of the active compound, thetimes of evaluation and the results can be seen from the following Table7:

TABLE 7 (Phaedon larvae test) Active compound Degree ofconcentradestruction tions in in percent Active compounds percent after3 days (A) s CH3 0.1 0

ll (CH 0)zP-O-, I NN H (known) (ll) 01 CH; 0.1 100 f) 0.01 100(CHsO)2P-O I| II C (1) Cl CH3 0.1 100 H l 0.01 100 (C2H60)2PO I I| IICH3 (6) 01 CH: 0.1 100 Gila S 0063} 18(5) P O 02 5 III-N (5) 01 CE: 0.1100 l-C:H10\fi 0. 01 100 11.0 g NN TABLE 7-Continued Active compoundDegree of concentradestruction tions in in percent Active compoundspercent after3days (4) Cl OH: 0.1 100 S I I 0.01 100 II 0.001 70(CHaO)2PO- III-N CH2-CHCN (10) CzHs Cl CH: 0.1 100 l 0.01 100 [I 0.00195 PO- 021160 I CH2--CHzCN (7) Cl CH3 0.1 100 i-CaH1O S 0.01 100 \II0.001 25 P CH:

CH2CH2CN (3) 01 CH; 0.1 100 H 0.01 100 (CHaO)zPO- III-N (12) Cl CHa 0.1100 i I 0.01 100 (C2H5O)zP-O l NN (9) 02H, 01 CH; 0.1 100 i 0.01 100 PO-Cz 5 EXAMPLE 8 Myzus test (contact action) Solvent: 3 parts by weightacetone Emulsifier: 1 part by weight al'kylaryl polyglycol ether Toproduce a suitable preparation of active compound, 1 part by weight ofthe active compound is mixed with the stated amount of solventcontaining the stated amount of emulsifier and the concentrate isdiluted with water to the desired concentration.

Cabbage plants (Brassica oleracea) which have been heavily infested withpeach aphids (Myzus persicae) are sprayed with the preparation of theactive compound until dripping wet.

After the specified periods of time, the degree of de struction isdetermined as a percentage: 100% means that all the aphids are killedwhereas 0% means that none of the aphids are killed.

16 The active compounds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 8:

TABLE 8 (Myzus test) I Active compound Degree of concentradestructiontions in in percent Active compounds percent after 1 day (CH O)zP-O- NIH (known) (B) (Hz 0.1 99 0.01 40 0.001 0 (C2H 0)2P0 NN H (known) (11)01- CH; 0.1 100 s I 0. 01 95 II 0. 001 60 (CHs0)2 IIII\ CH5 (1) 01 (H 0.1 100 S I 0.01 100 ll 0.001 95 (C2H50)zP-O 1|IN CH3 (6) Cl CH3 0. 1 10002H; S 0. 01 100 0 001 100 PO 0 0001 100 02 5 I|qN I (5) v Cl CH: 0.1100 i-CzH O s I l 0. 01 100 II 0. 001 100 /PO- 0. 0001 CH: f

(2)"--- Cl CH 0.1 100 S I 0.01 08 ll 0. 001 (CzH5O)zPO-- IIIN G Hz-OH-CN (10). Cl CH 0. 1 C2H5 S 0. 01 100 II 0.001 08 /PO 0,1150 f CHPCHz-CN(7)---. 01 CH; 0.1 100 1-CaH1O S 0.01 100 I 0. 001 99 P-O- om f EXAMPLE9 Tetranychus test/ resistant Solvent: 3 parts by weight acetoneEmulsifier: 1 part by weight alkylaryl polyglycol ether To produce asuitable preparation of active compound, 1 part by weight of the activecompound is mixed with the stated amount of solvent containing thestated amount of emulsifier and the concentrate' 'so obtained is dilutedwith water to the desired concentration.

Bean plants (Phaseolus vulgaris), which have a height of approximately10-30 cm., are sprayed with the preparation of the active compound untildripping wet. These bean plants are heavily infested with spider mites(Terranychus urticae) in all stages of development.

After the specified periods of time, the elfectiveness of thepreparation of active compound is determined by counting the dead mites.The degree of destruction thus obtained is expressed as a percentage:100% means that all the spider mites are killed whereas means that noneof the spider mites are killed.

The active com unds, the concentrations of the active compounds, theevaluation times and the results can be seen from the following Table 9:

The process of this invention is illustrated in and by the followingpreparative Examples.

EXAMPLE 10 Ha-CH: C N (VH8) 130 g. of ethyl acetoacetate are added to asolution of 85 g. of cyanoethylhydrazine in 400 ml. of ethanol, in thecourse of which the temperature rises to 55 C.', the solution is furtherstirred overnight, seeded and cooled to 0 C. The precipitate which hasseparated out is filtered off and dried over clay. 119 g. (79% oftheory) of 1-cyanoethyl-3-methyl-5-hydroxypyrazole of melting point 110C. are obtained.

45 g. (0.3 mole) of the product obtained under (a), dissolved in 300 ml.of methylene chloride, are treated with 84 g. of sulfonylchloride at theboil. The mixture is kept for one hour at the boil, the volatileconstituent is distilled off and the residue is subjected to slightdistillation. 62 g. (94% of theory) of the desired substance ofrefractive index u 1.5095 are obtained.

Cl (Ha 28 g. (0.15 mole) of 0,0-diethylthionophosphoric acid esterchloride are added dropwise to a mixture of 28 g. (0.15 mole) of 1cyanoethyl-3-methyl 4-chloro-5-hydroxypyrazole and 23 g. of potassiumcarbonate in 200 ml. of acetonitrile, in the course of which theinternal temperature rises to 23-31 C. Thereafter, the reaction mixtureis heated to 60-70 C. for 3 hours while stirring, cooled, poured intowater and extracted by shaking with benzene. The organic phase is washedwith water and dried, the solvent is stripped otf under reduced pressureand the residue is subjected to slight distillation. 44 g. (87% oftheory) of 0,0-diethyl-O-(l-cyanoethyl-B-methyl4-chloropyrazol-5-yl)-thionophosphoric acid ester of refractive index n1.5050 are obtained.

1,3-din ethyl-4-chloro-S-hydroxypyrazole (melting point 170-l71 C.) isprepared from ethyl acetoacetate and monomethylhydrazine, withsubsequent chlorination, as set forth in Example 10(a), (b), (c).

b 01 C s H:

N- 43H: (I)

19 g. (0.1 mole) of 0,0-diethylthionophosphoric acid ester chloride areadded to 15 g. (0.1 mole) of 1,3-dimethyl-4-chloro-5-hydroxypyrazole asproduced in (a) and 15 g. of potassium carbonate in ml. of acetonitrile,in the course of which the temperature rises to 26-38 C. Thereafter thebatch is warmed to 60' C. for 3 hours while stirring, cooled, pouredinto water and extracted by shaking with benzene. The organic phase iswashed with water, the solvent is removed under reduced pressure and theresidue is subjected to "slight distillation."

26 g. (87% of theory) of 0,0-diethyl-0-(1,3-dimethyl-4-chloro-pyrazol-5-yl)-thionophosphoric acid ester of refractive index u1.4980 are obtained.

The following compounds are prepared in a manner TABLE-CMil1I1edanalogous to that described in the, preceding Examples: Yield v Physical(percent Structure properties of theory) Physical g g g 12 01 CH.nn:1.5529 as Structure properties oi theory) H t H 3 01 on, nn":1.5648so 0 i i (QHsOhP-O- I I Melting point.

. It will be appreciated that the instant specification and (4) 5 T 77examples are set forth by way of illustration and not limitation, andthat various modifications and changes may be made without departingfrom the spirit and scope I of the present invention. CHPCH -CN What isclaimed is:

1. An O-pyrazolothionophosphoric (phosphonic) acid C] 111314215105 90ester of the formula i-CzHzO S l {L R S or CIHZ Ca, t CH: RO III--N v(I) o 01 on. un":1.5070 so R" fi in which R is alkyl or alkoxy each of.1 to 6 carbon atoms, R is alkyl of 1 to 6 carbon atoms, and

CH1 I R" is alkyl or cyanoalkyl wherein the alkyl radical of each is of1 to 6 carbon atoms, or phenyl. (7) I 01 CH; nn"=1.5155 83 2. A compoundaccording to claim 1 in which R is lower alkyl or alkoxy, R' is loweralkyl and R" is cyano- -0 ethyl, methyl, ethyl or phenyl. Q 40 3. Thecompound according to claim 1 wherein such GHPCHFCN compound is0,0-diethy1-O-(1,3-dimethyl-4-chlor0-pyrav zol-S-yl)-thionophosphoricacid ester of the formula (8) 01 OH; nn"z1. 5532 80 (CHa)2CH-O S l 01(3Ha {L l i l l CIL/ N z sO)2PO- NN l I (13H:

4. The compound according to claim 1 wherein such compound isO-isopropyl-O-(1,3-dimethyl-4-chloro-pyra- 01 CH, nn":1- 5591 8zol-S-yl)-methanethionophosphonic acid ester of the forv 5. The compoundaccording to claim 1 wherein such 1o 01 CH; nn":1.5180 81 compound isO-cthyl-O-(1,3-dimethyl-4-chloro-pyraz0l-5- fiyl)-ethanethionophosphonic acid ester of the formula PO- 0130/: 01 cmCHz-CHr-CN 2H|0\fi I /P0 (11).-. a 01 cm nn? :1.5105 '77 I l a v 7 CH3(6) a ):P0 v

c Y 6. The compound according to claim 1 wherein s uch CH! compound is0-ethyl-0-(1-cyanoethyl-3-methy1-4-chloro 21 22 pyrazol-S-yl)ethanethionophosphonic acid ester of the References Cited immula UNITEDSTATES PATENTS 02H, S 1}? 2,754,244 7/1956 Gysin ct a1. 2611-310 R g3,216,894 11/1965 Lorcnz ct a1 260-310 R 0241. N z j FOREIGN PATENTSm-cm-cn (11 728,152 2/1966 Canada 260-310 R 7. The compound according toclaim 1 wherein such 930,212 7/1955 Germany 260310A compound is0,0-dimethyl-0-(1,3-dimethyl-4-chloro-py- 10razol-S-yl)-thionophosphoric acid ester of the formula NATALIE TROUSOF-Pnmary Exam" 8 01 US. 01. X.R. 424200 (CHaOhP-O UNITED STATES PATENTOFFICE CERTIFICATE OF CORRECTION 1 2 197A Patent No. 5 557 Dated Ju y 5Inventor(s) It is certified that error appears in the above-identifiedpatent and that said Letters Patent vare .hereh icmzr ted as shounqbeloi Col. 5, line'54, after "aryl" correct spelling of "sulfonates",

I Col. 8, Table 2, Compound'(4) ,under column "LT change "69" Col. 8,Table 2, Compound (1), under column "L'l cancel "60",seeondoccurrence,.and substitute 120 Col. 9, Table 3, Compound (5), second column ofTable, cancel "0.92" and substitute 0.02

Col. ll, Table 5, Compound (5),last column of Table, cancel "02" andsubstitute 20 Col. ll, Table 5, Compound (2),- last column of Table,cancel "20" and substitute 0 Col. 13, Table 6, Compound (5), last columnof Table, cancel 0 "16, and substitute lOO Col. 17, Table 9, Compound(5) in the formula, cancel "H and substitute CH Signed and sealed this3rd day of December 1974.

( EAL) Attest:

McCOY M. GIBSON JR. C. MARSPALL DANN Attesting Officer Cormnissioner ofPatents FORM Po-wso USCOMM'DC wand? U.S, GOVERNMENT PRINTING OFFICE 930

